The central theme of the proposed synthetic methods is the generation of carbonium ions by the removal of thiophenoxide by cuprous ion, often in the presence of an amine, from suitable molecules such as readily available thioacetals, thioketals, or orthothioesters. Proximate reactions of these cations include proton loss to give alkenes or dienes, intramolecular capture leading to ring compounds, substitution into or addition to alkenes or dienes, cyclopropane openings and 1, 2-shifts. The largest section proposes preparation of a variety of sulfur-substituted 1,3-dienes and demonstrations of their versatility, particularly in Diels-Alder reactions; other improvements in the latter reaction are also suggested. The dienes will also serve as precursors of the potential annelating agent. Alpha-thiophenoxyvinyl methyl ketone, and of vinyl gem-dithiophenoxycyclopropanes which, by thermal or copper (I)-induced rearrangment, should provide a variety of cyclopentanones. Methods are suggested for the conversion of enones into 1,3-dithiophenoxy-1-alkenes and the utilization of their conjugate bases as beta-enone anion equivalents. The copper-sulfer technology will also be applied to the synthesis of furans and indolizines and to new ring expansions. Syntheses of a number of natural products will be attempted in order to demonstrate the utility of these techniques.